CN104371066B - PH and temperature dual-sensitivity intelligent nanogel and preparation method thereof - Google Patents
PH and temperature dual-sensitivity intelligent nanogel and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000009977 dual effect Effects 0.000 claims abstract description 60
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 43
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 38
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 15
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims abstract description 12
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims abstract description 12
- 229920000053 polysorbate 80 Polymers 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 150000003839 salts Chemical class 0.000 claims description 34
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 241000233803 Nypa Species 0.000 claims description 12
- 235000005305 Nypa fruticans Nutrition 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- YICILWNDMQTUIY-UHFFFAOYSA-N 2-methylidenepentanamide Chemical compound CCCC(=C)C(N)=O YICILWNDMQTUIY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 235000019256 formaldehyde Nutrition 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 124
- 239000000017 hydrogel Substances 0.000 description 20
- 238000007334 copolymerization reaction Methods 0.000 description 16
- 230000004044 response Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- 238000001879 gelation Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 235000013339 cereals Nutrition 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000004936 stimulating effect Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000013270 controlled release Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000012703 microemulsion polymerization Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000003745 diagnosis Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000012673 precipitation polymerization Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
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- 230000035699 permeability Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NORSCOJMIBLOFM-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(=O)OCCO NORSCOJMIBLOFM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000002210 biocatalytic effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 238000006073 displacement reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- MVKYQTGCKJXECD-UHFFFAOYSA-N ethane-1,2-diol;prop-1-ene Chemical group CC=C.CC=C.OCCO MVKYQTGCKJXECD-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
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- 235000010413 sodium alginate Nutrition 0.000 description 1
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- Medicinal Preparation (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cosmetics (AREA)
Abstract
The invention provides a pH and temperature dual-sensitive intelligent nanogel and a preparation method thereof. The method comprises the following steps: adding itaconic acid into a sodium hydroxide solution to obtain a partially neutralized itaconic acid aqueous solution; adding acrylamide, N-isopropyl acrylamide and a cross-linking agent into a partially neutralized itaconic acid aqueous solution, and stirring to obtain a transparent monomer mixed solution; adding the transparent monomer mixed solution into a mixed solvent containing an oil-soluble solvent and a Span80/Tween80 composite surfactant, stirring, heating to 40-60 ℃, and adding an oxidant and a reducing agent to obtain a transparent or semitransparent intelligent nano-gel reverse microemulsion; and demulsifying and precipitating the intelligent nano gel reverse microemulsion by using ethanol, washing, drying and grinding to obtain the pH and temperature double sensitive intelligent nano gel. The invention also provides the pH and temperature dual-sensitive intelligent nanogel prepared by the preparation method, and the nanogel has good pH and temperature dual sensitivity.
Description
Technical field
The present invention relates to a kind of intelligent nano-gel and preparation method thereof, sensitive particularly to a kind of pH and temperature dual
Property intelligent nano-gel and preparation method thereof, belongs to nano material and preparing technical field.
Background technology
Intelligent nano-gel (Intelligent nanogel) be particle diameter at 1-1000nm, can respond environmental stimuli occur turn mutually
The hydrogel particle become, the stimulating responsive nanogel that is therefore otherwise known as (Stimulus responsive nanogel).
Environmental stimuli generally includes small environment temperature, decentralized medium pH and the change of ionic strength, Yi Jiguang, magnetic field,
Specific chemical substance or biological substance etc..Occurring during phase in version, the volume of intelligent nano hydrogel, containing
The physics such as the water yield, refraction index, colloidal stability, soft durometer, the internal permeability of gel network, hydrophilicity hydrophobicity
Chemical property all can occur to change accordingly.In addition, intelligent nano hydrogel also has following features:
1, can be dispersed in aqueous medium, form stable colloidal dispersion；
2, inside has cross-linked structure, and stability is stablized than other polymer nano-particle (such as polymer micelle etc.)
Property want height；
3, specific surface area is big, and the functional group on surface coupling can have the component of specific function；
4, water content is high, is similar to biological tissue, has good biocompatibility；
5 as other nano particle, easily crosses biological barrier；
6, the speed producing response is stimulated to be inversely proportional to its size to external world due to intelligent aqueous gel, thus intelligent
Nano-hydrogel stimulates the speed producing response the fastest to external world.
Nearly ten years along with the development of nanosecond science and technology, biomedicine and intellectual material, intelligent nano-gel carries at medicine
With controlled release, medical diagnosis, biology sensor, biomaterial, catalyst carrier, adsorb with separate, water process
Show tempting application prospect with fields such as oil-gas field developments, therefore suffer from highest attention both domestic and external.
Can start to receive publicity to the most triple dual intelligent gels stimulating generation response in recent years, wherein, research
Most is pH/ temperature dual stimulating responsive hydrogel, this is because temperature and pH are in biological and chemical system
Highly important two kinds of environmental conditions.
The preparation method that pH/ temperature dual sensitiveness intelligent gel uses at present will have different stimulated response
Polymers compositions is incorporated into the polymer of hydrogel by methods such as random copolymerization method, grafting copolymerization process and core shell structure methods
In network, polymerization implementation mostly is emulsifier-free emulsion polymerization, emulsion polymerization, polymerisation in solution, precipitation polymerization and photopolymerization,
Research emphasis concentrates on pH and temperature response performance, rheological property and the intelligent gel structure etc. of intelligent gel, should
For medicine conveying and controlled release, medical diagnosis, biology sensor, catalyst carrier etc..
Wherein, Serrano-Medina use emulsifier-free emulsion polymerization be prepared for pH and temperature dual sensitiveness, have core-
The micro-/ nano gel of shell structure, by being incorporated into temperature sensitive by pH sensitive groups-2-methacryloxy benzoic acid
Property poly-N-isopropyl acrylamide (PNIPAm) in, form pH and the gel of temperature dual sensitiveness.
Polyacrylic acid-grafting-poly-N-isopropyl acrylamide hydrogel that Durand uses two-step method to prepare has shown
The thermic thickening behavior of interest.
Zhao Changwen uses degradable, the L-glutamic acid of pH sensitiveness and poly-(the N-isopropyl third of Thermo-sensitive
Acrylamide-HEMA), it is prepared for degradable doubling sensitivity hydrogel by photopolymerization, its
PH and temperature sensitivity are preferable.
Ju Hee Kyung and Zhang Gaoqi is respectively adopted polymerisation in solution and is prepared for by crosslinking poly-N-isopropyl acryloyl
Doubling sensitivity that amine (PNIPAm) and linear sodium alginate (SA) form, the water-setting with half interpenetrating network structure
Glue, this gel demonstrates preferable mechanical strength and preferable pH/ temperature-responsive.
Zhang Jing employing photopolymerization is prepared for be had mutually by what polyacrylic acid and NIPA were formed
Wearing the intelligent gel of network structure, the permeability of this gel mould can occur significantly to become by pH and the regulation of temperature
Change.
Looking into Liu Sheng etc. uses precipitation polymerization to be prepared for having the pH/ temperature dual thorn of interpenetrating polymer networks (IPN) structure
Swash response hollow Nano hydrogel, find hollow Nano hydrogel to be loaded medicine by adjusting ambient temperature, and
By changing the speed of environmental pH energy Drug controlled release.
With above-mentioned prepare nanogel method compared with, microemulsion is that thermodynamically stable transparent or semitransparent colloid divides
Prose style free from parallelism system, its dispersion size is nanoscale, therefore uses micro-emulsion polymerization can prepare particle diameter little, narrow diameter distribution
Nanogel.
Wherein, Bouillt etc. uses acrylamide and acrylic acid to be monomer, has synthesized tool by conversed phase micro emulsion copolymerization method
PH stimulating responsive, two classes are had to have the nano-hydrogel of different chemical structures: a class is by two kinds of monomers and crosslinking
Polyacrylic acid-acrylamide copolymer nano-hydrogel that agent copolymerization is formed, another kind of is to be polymerized respectively by two kinds of monomers
The nanometer water-setting with interpenetrating polymer networks (IPN) structure that the both of which polymers obtained is formed by hydrogen bond action
Glue.
Deen etc. make N-acryloyl group-N methyl piperazine and methyl methacrylate copolymer in Reverse Microemulsion System
Prepare the nano-hydrogel with pH stimulating responsive, find that nano-hydrogel occurs swelling in acidic aqueous solution,
And produce in alkaline solution and shrink.
Hou Wei etc. use conversed phase micro emulsion copolymerization to be prepared for poly-2-hydroxy ethyl methacrylate-methacrylic acid copolymer
Hydrogel, have studied its rheological property, finds hydrogel composition, hydrogel concentration, the pH value springform to gel
Amount impact is bigger.
Fernandez etc. use conversed phase micro emulsion copolymerization to be prepared for the poly-N-isopropyl acrylamide with temperature sensitivity
(PNIPAm), finding its swelling rate and go swelling rate all very fast, elastic modelling quantity and Young's modulus are above using
Hydrogel prepared by commonsense method.
But, the nanogel using conversed phase micro emulsion copolymerization to prepare the most both at home and abroad is pH sensitiveness or temperature
Degree sensitiveness nanogel, uses conversed phase micro emulsion copolymerization method to prepare pH/ temperature dual stimulating responsive intelligent nano and coagulates
Glue does not still have relevant report.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of pH and temperature dual sensitiveness intelligence is received
The preparation method of rice gel, using NIPA in this preparation method is that temperature sensitive monomer, itaconic acid are
PH sensitive monomer, acrylamide is Hydrophilic nonionic monomer, use conversed phase micro emulsion copolymerization method prepare pH and
Temperature dual sensitiveness intelligent nano-gel, the pH being improved intelligent nano-gel by 2 carboxyls of itaconic acid molecule is rung
Ying Xing, utilizes intelligent gel to stimulate the characteristic that the speed producing response is inversely proportional to its size to external world, by adjusting
Control conversed phase micro emulsion copolymerization response parameter regulates and controls the particle diameter of intelligent nano-gel, thus regulates and controls intelligent nano hydrogel pair
Environmental stimuli produces the speed of response.The method specifically includes following steps:
Step one: in ice bath, itaconic acid is slowly added in the sodium hydroxide solution that concentration is 10wt%, stirring
0.5-2h, obtains the itaconic acid aqueous solution that part neutralizes；
Wherein, the mol ratio of described itaconic acid and NaOH is 1:0.8-1.4；
Step 2: the itaconic acid that acrylamide, NIPA and crosslinking agent join part neutralization is water-soluble
In liquid, stir 20-40min, obtain transparent monomers mixed solution；
Wherein, the mass ratio of described itaconic acid and described acrylamide is 4:6-6:4, and described itaconic acid and described N-are different
The mass ratio of propylacrylamide is 3:7-7:3, and the consumption of described crosslinking agent is itaconic acid, acrylamide and N-isopropyl
The 0.1-0.6% of the gross mass of base acrylamide；
Step 3: transparent monomers mixed solution is joined containing oil-dissolving solvent and Span80/Tween80 composite table
In the mixed solvent of face activating agent, stir 20-40min, form transparent reverse micro emulsion, be then gradually heating to
40-60 DEG C, add Oxidizing and Reducing Agents, react 3-5 hour, obtain transparent or semitransparent intelligent nano-gel
Reverse micro emulsion；
Wherein, the mass ratio of Span80 and Tween80 is 3-6:2-4, and the consumption of oxidant is itaconic acid, acryloyl
The 0.4-1.8% of the gross mass of amine and NIPA, the mol ratio of Oxidizing and Reducing Agents is 1-2:1；
Step 4: described intelligent nano-gel reverse micro emulsion ethanol breakdown of emulsion is precipitated, acetone washing precipitation 3-5 time,
60 DEG C of freeze-day with constant temperature 10h, product is dried, finely ground after obtain white intelligent nano-gel powder, this white intelligence is received
Rice gel powder is pH and temperature dual sensitiveness intelligent nano-gel.
In the pH of present invention offer and the preparation method of temperature dual sensitiveness intelligent nano-gel, it is preferable that use
Oil-dissolving solvent selected from hexamethylene, atoleine, white oil and petroleum ether.
In the pH of present invention offer and the preparation method of temperature dual sensitiveness intelligent nano-gel, it is preferable that work as step
In rapid one add 10mL-20mL sodium hydroxide solution time, transparent monomers mixed solution is joined by step 3 containing
In the mixed solvent of the oil-dissolving solvent of 100g and the Span80/Tween80 complexed surfactant of 8-16g.
In the pH of present invention offer and the preparation method of temperature dual sensitiveness intelligent nano-gel, it is preferable that use
Crosslinking agent selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, diethylene glycol double methacrylate,
Tirethylene glycol double methacrylate and polyethyleneglycol diacrylate.
In the pH of present invention offer and the preparation method of temperature dual sensitiveness intelligent nano-gel, it is preferable that use
Oxidant selected from ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate.
In the pH of present invention offer and the preparation method of temperature dual sensitiveness intelligent nano-gel, it is preferable that use
Reducing agent close Sodium Thiosulfate selected from sodium hydrogensulfite, sodium sulfite, sodium thiosulfate and formaldehyde.
In the pH of present invention offer and the preparation method of temperature dual sensitiveness intelligent nano-gel, it is preferable that intelligence
The average grain diameter of nanogel reverse micro emulsion is 40-80nm.
Present invention also offers a kind of pH and temperature dual sensitiveness intelligent nano-gel, it is above-mentioned pH and temperature
The preparation method of degree doubling sensitivity intelligent nano-gel prepares.
In the pH of the present invention and temperature dual sensitiveness intelligent nano-gel, it is preferable that this pH and temperature dual are quick
The gel strength of perception intelligent nano-gel is 5-15Pa s.
In the pH of the present invention and temperature dual sensitiveness intelligent nano-gel, it is preferable that this pH and temperature dual are quick
The equilibrium water absorption of perception intelligent nano-gel is 80-500g/g, inhales the balance of the NaCl solution that concentration is 5wt%
Salt rate is 25-35g/g, is the CaCl of 5wt% to concentration2The balance salt absorbing rate of solution is 10-20g/g, to concentration is
The MgCl of 5wt%2The balance salt absorbing rate of solution is 15-25g/g.
In order to better illustrate pH and the performance of temperature dual sensitiveness intelligent nano-gel of the present invention, according to following
Method of testing has carried out water absorption rate mensuration to the gel of the present invention, salt absorbing rate measures, gel strength measures, pH response
Property measure, temperature-responsive measure and particle size determination, concrete assay method is as follows:
Water absorption rate measures:
The intelligent nano-gel of dry, the finely ground present invention of precise a certain amount of (0.5g), puts into beaker
(500mL) in, add distilled water (500mL), the most fully absorb water, until the intelligent nano of the present invention coagulates
Glue water suction is saturated, with the unadsorbed water of Bag filter, to substantially anhydrous drippage.After measuring fully water suction, intelligence is received
The weight of rice gel, calculates water absorption rate according to formula (1).
Water absorption rate=(m2-m1)/m1× 100% (1)
Wherein, m1For the quality of intelligent nano-gel before water suction, unit is g, m2For intelligent nano-gel after water suction
Quality, unit is g.
Salt absorbing rate measures:
Accurately weigh the intelligent nano-gel of dry, the finely ground present invention of a certain amount of (0.5g), put into beaker
(100mL), in, it is then respectively adding NaCl, MgCl that concentration is 5%2And CaCl2Solution (100mL), in room temperature
Under the conditions of fully inhale salt solution, until the present invention intelligent nano-gel inhale salt water saturation, with the unadsorbed salt of Bag filter
Water, dripping to basic salt-free water.The weight of intelligent nano-gel after mensuration fully suction salt solution, according to formula (2)
Calculate salt absorbing rate.
Salt absorbing rate=(m2-m1)/m1× 100% (2)
Wherein, m1For the quality of intelligent nano-gel before suction salt solution, unit is g, m2For intelligent nano after suction salt solution
The quality of gel, unit is g
The mensuration of gel strength:
Accurately weigh dry, the finely ground intelligent nano-gel of a certain amount of (0.2g), put in beaker (200mL), then
Add distilled water (200mL), the most fully absorb water, after gelinite reaches water suction balance, use cloth bag mistake
Filter unadsorbed water, to anhydrous drippage, then use the apparent viscosity of rotary viscosity design determining water absorbent gel body, i.e.
Gel strength for the intelligent nano-gel water absorbent gel body of the present invention.
PH response measures:
Accurately weigh dry, the finely ground intelligent nano-gel of a certain amount of (0.2g), put in beaker (200mL), then
Add distilled water (200mL), fully absorb water under condition of different pH, until intelligent nano-gel water suction is saturated, use
The water that Bag filter is unadsorbed, to substantially anhydrous drippage.Measure intelligent nano-gel weight after fully water suction, press
The water absorption rate of intelligent nano-gel under condition of different pH is calculated according to formula (1).
Temperature-responsive measures:
Accurately weigh dry, the finely ground intelligent nano-gel of a certain amount of (0.2g), put in beaker (200mL), then
Add distilled water (200mL), fully absorb water under condition of different temperatures, until intelligent nano-gel water suction is saturated.With
The water that Bag filter is unadsorbed, to substantially anhydrous drippage.Measure intelligent nano-gel weight after fully water suction, press
The water absorption rate of intelligent nano-gel under condition of different temperatures is calculated according to formula (1).
The mensuration of particle diameter:
Use FEI Co. Tecnai G2 F20S-TWIN Flied emission transmission electron microscope of the U.S. (TEM) to observe intelligent nano to coagulate
Glue granular size and microscopic pattern, by reverse micro emulsion sample with after hexamethylene dilution certain multiple, dye with phosphotungstic acid,
Then dip-coating is on copper mesh, is placed on sample stage after drying, and is loaded into electron microscopic sample room, and imaging is also taken pictures, passed through
Photoshop software computational intelligence nanogel biocatalytic particle particle size.
The pH of present invention offer and temperature dual sensitiveness intelligent nano-gel and preparation method thereof, have following useful
Effect:
The present invention uses conversed phase micro emulsion copolymerization to prepare intelligent nano-gel, and microemulsion is thermodynamically stable transparent or half
Transparent colloidal dispersion system, its dispersion size is nanoscale, uses conversed phase micro emulsion copolymerization to prepare transparent or half
Transparent, average grain diameter is pH and the temperature dual sensitiveness intelligent nano-gel of 40-80nm, and micro-emulsion polymerization
Course of reaction is stable, reaction rate is fast.
Owing to conversed phase micro emulsion copolymerization reaction is to carry out in nano grade discontinuous phase drop, it is not similar to precipitation polymerization method
Or the nucleation process of emulsion polymerization, therefore the crosslinking points distribution of the nanogel of the preparation method synthesis of the present invention is more equal
Even, advantageously form more perfect three-dimensional net structure.
Employing NIPA be temperature sensitive monomer, itaconic acid be pH sensitive monomer, acrylamide is parent
Aqueous non-ionic monomer, is improved the pH response of intelligent nano-gel, utilizes intelligence by 2 carboxyls of itaconic acid molecule
Energy gel stimulates the characteristic that the speed producing response is inversely proportional to its size to external world, by regulation and control reverse micro emulsion
Polymerization reaction parameter regulates and controls the particle diameter of intelligent nano-gel, thus regulates and controls intelligent nano hydrogel and stimulate generation to external world
The speed of response.
Improve whole intelligence at the gel ionic of present invention offer and the addition of non-ionic hydrophilic component to coagulate
The hydrophilic/hydrophobic ratio of glue network, the hydrogen bond number formed with hydrone increases, and needs relatively multi-energy could destroy these
Hydrogen bond, improves the phase transition temperature of intelligent gel, expands the transition temperature range of intelligent gel.
The intelligent nano-gel that the present invention provides has good water suction and inhales salt performance and higher gel strength, at pH
Value is for 4-10 and all shows stronger pH and temperature-responsive at 30-50 DEG C, is expected to be applied to medicine conveying
Inhale with controlled release, medical diagnosis, biology sensor, biomaterial, catalyst carrier, heavy metal ion and dyestuff
Attached with separate, water process and the field such as the oil field displacement of reservoir oil and profile control in.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
Embodiment 1
Present embodiments providing a kind of pH and temperature dual sensitiveness intelligent nano-gel and preparation method thereof, this is prepared
Method comprises the following steps:
The NaOH that mass concentration is 10% that the itaconic acid of 4.0625g is slowly added in ice bath 10mL is molten
In liquid, it is sufficiently stirred for, reacts 0.5h, obtain the itaconic acid aqueous solution that part neutralizes；
By the acrylamide of 6.0938g, the NIPA of 1.7411g and the N of 0.0595g, N '-methylene
Bisacrylamide joins in the itaconic acid aqueous solution that part neutralizes, uniform stirring 20min, obtains transparent monomers mixing
Solution；
Above-mentioned transparent monomers mixed solution is joined Span80's and 3.2g of the hexamethylene equipped with 100g, 4.8g
In the there-necked flask of Tween80, uniform stirring 20min, form transparent reverse micro emulsion, be then gradually heating to
40 DEG C, the sodium hydrogensulfite of the ammonium persulfate and 0.0434g that add 0.0952g causes conversed phase micro emulsion copolymerization reaction,
React 5 hours, obtain intelligent nano-gel reverse micro emulsion transparent or semitransparent, that average grain diameter is 50nm；
The intelligent nano-gel reverse micro emulsion of synthesis is precipitated with ethanol breakdown of emulsion, acetone washing precipitation 3 times, put into baking
In case, 60 DEG C of freeze-day with constant temperature 10h, finely ground, obtain white intelligent nano-gel powder, this powder be described pH and
Temperature dual sensitiveness intelligent nano-gel.
Absorb water to the pH of the present embodiment and temperature dual sensitiveness intelligent nano-gel, inhale the performance test of salt etc.,
Result shows, the equilibrium water absorption of the gel of the present embodiment is 120g/g, to the NaCl solution that concentration is 5wt%
Balance salt absorbing rate is 30g/g, CaCl to concentration 5wt%2The balance salt absorbing rate of solution is 14g/g, is 5wt% to concentration
MgCl2The balance salt absorbing rate of solution is 18g/g；And the gel strength of the gel of the present embodiment is 13Pa s,
PH value be 4-10 and 30-50 DEG C show stronger pH and temperature-responsive.
Embodiment 2
Present embodiments providing a kind of pH and temperature dual sensitiveness intelligent nano-gel and preparation method thereof, this is prepared
Method comprises the following steps:
The NaOH that mass concentration is 10% that the itaconic acid of 4.6429g is slowly added in ice bath 20mL is molten
In liquid, it is sufficiently stirred for, reacts 2h, obtain the itaconic acid aqueous solution that part neutralizes；
By the acrylamide of 4.6429g, the NIPA of 10.8334g and 0.1207g ethylene glycol bis propylene
Acid esters joins in the itaconic acid aqueous solution that part neutralizes, and uniform stirring 40min obtains transparent monomers mixed solution；
Above-mentioned transparent monomers mixed solution is joined the atoleine equipped with 100g, the Span80 of 10.6667g and
In the there-necked flask of the Tween80 of 5.3333g, uniform stirring 40min, form transparent reverse micro emulsion, then
Being gradually heating to 60 DEG C, the formaldehyde of the potassium peroxydisulfate and 0.0230g that add 0.0805g closes Sodium Thiosulfate and causes anti-phase
Micro-emulsion polymerization reacts, and reacts 4 hours, obtains intelligent nano transparent or semitransparent, that average grain diameter is 60nm and coagulates
Glue reverse micro emulsion；
The intelligent nano-gel reverse micro emulsion of synthesis is precipitated with ethanol breakdown of emulsion, acetone washing precipitation 5 times, put into baking
In case, 60 DEG C of freeze-day with constant temperature 10h, finely ground, obtain white intelligent nano-gel powder, this powder be described pH and
Temperature dual sensitiveness intelligent nano-gel.
Absorb water to the pH of the present embodiment and temperature dual sensitiveness intelligent nano-gel, inhale the performance test of salt etc.,
Result shows, the equilibrium water absorption of the gel of the present embodiment is 80g/g, putting down the NaCl solution that concentration is 5wt%
Weighing apparatus salt absorbing rate is 25g/g, CaCl to concentration 5wt%2The balance salt absorbing rate of solution is 10g/g, is 5wt% to concentration
MgCl2The balance salt absorbing rate of solution is 15g/g；And the gel strength of the gel of the present embodiment is 15Pa s,
PH value be 4-10 and 30-50 DEG C show stronger pH and temperature-responsive.
Embodiment 3
Present embodiments providing a kind of pH and temperature dual sensitiveness intelligent nano-gel and preparation method thereof, this is prepared
Method comprises the following steps:
In ice bath, the itaconic acid of 2.7083g is slowly added into the sodium hydroxide solution that 10mL mass concentration is 10%
In, it is sufficiently stirred for, reacts 1.5h, obtain the itaconic acid aqueous solution that part neutralizes；
The polyethylene glycol of the acrylamide of 1.8055g, the NIPA of 1.1607g and 0.0057g is double
Acrylate joins in the itaconic acid aqueous solution that part neutralizes, uniform stirring 30min, obtains transparent monomers mixing molten
Liquid；
Above-mentioned transparent monomers mixed solution is joined Span80's and 6.4g of the white oil equipped with 100g, 9.6g
In the there-necked flask of Tween80, uniform stirring 30min, form transparent reverse micro emulsion, be then gradually heating to
50 DEG C, the sodium sulfite of the ammonium persulfate and 0.0342g that add 0.0681g causes conversed phase micro emulsion copolymerization reaction, instead
Answer 4 hours, obtain intelligent nano-gel reverse micro emulsion transparent or semitransparent, that average grain diameter is 40nm；
The intelligent nano-gel reverse micro emulsion of synthesis is precipitated with ethanol breakdown of emulsion, acetone washing precipitation 5 times, put into baking
In case, 60 DEG C of freeze-day with constant temperature 10h, finely ground, obtain white intelligent nano-gel powder, this powder be described pH and
Temperature dual sensitiveness intelligent nano-gel.
Absorb water to the pH of the present embodiment and temperature dual sensitiveness intelligent nano-gel, inhale the performance test of salt etc.,
Result shows, the equilibrium water absorption of the gel of the present embodiment is 500g/g, to the NaCl solution that concentration is 5wt%
Balance salt absorbing rate is 35g/g, CaCl to concentration 5wt%2The balance salt absorbing rate of solution is 20g/g, is 5wt% to concentration
MgCl2The balance salt absorbing rate of solution is 25g/g；And the gel strength of the gel of the present embodiment is 5Pa s,
PH value be 4-10 and 30-50 DEG C show stronger pH and temperature-responsive.
Embodiment 4
Present embodiments providing a kind of pH and temperature dual sensitiveness intelligent nano-gel and preparation method thereof, this is prepared
Method comprises the following steps:
The itaconic acid of 6.5g is slowly added in the sodium hydroxide solution that 20mL mass concentration is 10% by ice bath,
It is sufficiently stirred for, reacts 2h, obtain the itaconic acid aqueous solution that part neutralizes；
By the diethylene glycol of the acrylamide of 6.5g, the NIPA of 4.3333g and 0.0347g double third
Olefin(e) acid ester joins in the itaconic acid aqueous solution that part neutralizes, and uniform stirring 40min obtains transparent monomers mixed solution；
Above-mentioned transparent monomers mixed solution is joined Span80's and 6g of the petroleum ether equipped with 100g, 6g
In the there-necked flask of Tween80, uniform stirring 40min, form transparent reverse micro emulsion, be then gradually heating to
55 DEG C, the sodium thiosulfate of the sodium peroxydisulfate and 0.1726g that add 0.3120g causes conversed phase micro emulsion copolymerization reaction,
React 4 hours, obtain intelligent nano-gel reverse micro emulsion transparent or semitransparent, that average grain diameter is 80nm；
The intelligent nano-gel reverse micro emulsion of synthesis is precipitated with ethanol breakdown of emulsion, acetone washing precipitation 4 times, put into baking
In case, 60 DEG C of freeze-day with constant temperature 10h, finely ground, obtain white intelligent nano-gel powder, this powder be described pH and
Temperature dual sensitiveness intelligent nano-gel.
PH and temperature dual sensitiveness intelligent nano-gel to the present embodiment absorb water, inhale the performance tests such as salt,
Result shows, the equilibrium water absorption of the gel of the present embodiment is 320g/g, to the NaCl solution that concentration is 5wt%
Balance salt absorbing rate is 32g/g, CaCl to concentration 5wt%2The balance salt absorbing rate of solution is 17g/g, is 5wt% to concentration
MgCl2The balance salt absorbing rate of solution is 22g/g；And the gel strength of the gel of the present embodiment is 8Pa s,
PH value be 4-10 and 30-50 DEG C show stronger pH and temperature-responsive.
Embodiment 5
Present embodiments providing a kind of pH and temperature dual sensitiveness intelligent nano-gel and preparation method thereof, this is prepared
Method comprises the following steps:
The itaconic acid of 3.75g is slowly added in the sodium hydroxide solution that 15mL mass concentration is 10% by ice bath,
It is sufficiently stirred for, reacts 1.5h, obtain the itaconic acid aqueous solution that part neutralizes；
By the tirethylene glycol of the acrylamide of 3.75g, the NIPA of 5.625g and 0.0525g double third
Olefin(e) acid ester joins in the itaconic acid aqueous solution that part neutralizes, and uniform stirring 30min obtains transparent monomers mixed solution；
Above-mentioned transparent monomers mixed solution is joined the hexamethylene equipped with 100g, the Span80 of 8.5714g and
In the there-necked flask of the Tween80 of 6.4286g, uniform stirring 30min, form transparent reverse micro emulsion, then
Being gradually heating to 45 DEG C, the sodium sulfite of the potassium peroxydisulfate and 0.0613g that add 0.1969g causes reverse micro emulsion to gather
Close reaction, react 5 hours, obtain intelligent nano-gel transparent or semitransparent, that average grain diameter is 45nm anti-phase micro-
Emulsion；
The intelligent nano-gel reverse micro emulsion of synthesis is precipitated with ethanol breakdown of emulsion, acetone washing precipitation 4 times, put into baking
In case, 60 DEG C of freeze-day with constant temperature 10h, finely ground, obtain white intelligent nano-gel powder, this powder be described pH and
Temperature dual sensitiveness intelligent nano-gel.
PH and temperature dual sensitiveness intelligent nano-gel to the present embodiment absorb water, inhale the performance tests such as salt,
Result shows, the equilibrium water absorption of the gel of the present embodiment is 110g/g, to the NaCl solution that concentration is 5wt%
Balance salt absorbing rate is 28g/g, CaCl to concentration 5wt%2The balance salt absorbing rate of solution is 13g/g, is 5wt% to concentration
MgCl2The balance salt absorbing rate of solution is 17g/g；And the gel strength of the gel of the present embodiment is 11Pa s,
PH value be 4-10 and 30-50 DEG C show stronger pH and temperature-responsive.
Above-described embodiment illustrates, the pH of the present invention and the preparation method of temperature dual sensitiveness intelligent nano-gel prepare
PH and temperature dual sensitiveness intelligent nano-gel there is good water suction, inhale salt performance, higher gel strength
And stronger pH and temperature-responsive.
Claims (10)
1. pH and a preparation method for temperature dual sensitiveness intelligent nano-gel, the method comprises the following steps:
Step one: in ice bath, itaconic acid is slowly added in the sodium hydroxide solution that concentration is 10wt%, stirring
0.5-2h, obtains the itaconic acid aqueous solution that part neutralizes；
Wherein, the mol ratio of described itaconic acid and NaOH is 1:0.8-1.4；
Step 2: the itaconic acid that acrylamide, NIPA and crosslinking agent join part neutralization is water-soluble
In liquid, stir 20-40min, obtain transparent monomers mixed solution；
Wherein, the mass ratio of described itaconic acid and described acrylamide is 4:6-6:4, and described itaconic acid and described N-are different
The mass ratio of propylacrylamide is 3:7-7:3, and the consumption of described crosslinking agent is itaconic acid, acrylamide and N-isopropyl
The 0.1-0.6% of the gross mass of base acrylamide；
Step 3: transparent monomers mixed solution is joined and is combined containing oil-dissolving solvent and Span80 and Tween80
In the mixed solvent of surfactant, stir 20-40min, form transparent reverse micro emulsion, the most gradually heat up
To 40-60 DEG C, add Oxidizing and Reducing Agents, react 3-5 hour, obtain transparent or semitransparent intelligent nano and coagulate
Glue reverse micro emulsion；
Wherein, the mass ratio of Span80 and Tween80 is 3-6:2-4, and the consumption of oxidant is itaconic acid, acryloyl
The 0.4-1.8% of the gross mass of amine and NIPA, the mol ratio of Oxidizing and Reducing Agents is 1-2:1；
Step 4: described intelligent nano-gel reverse micro emulsion ethanol breakdown of emulsion is precipitated, acetone washing precipitation 3-5 time,
60 DEG C of freeze-day with constant temperature 10h, obtain described pH and temperature dual sensitiveness intelligent nano-gel.
PH the most according to claim 1 and the preparation method of temperature dual sensitiveness intelligent nano-gel, its
In, described oil-dissolving solvent is selected from hexamethylene, atoleine, white oil and petroleum ether.
PH the most according to claim 1 and the preparation method of temperature dual sensitiveness intelligent nano-gel, its
In, when step one adds 10mL-20mL sodium hydroxide solution, transparent monomers mixed solution is added by step 3
The mixing entering Span80 and the Tween80 complexed surfactant to the oil-dissolving solvent containing 100g and 8-16g is molten
In agent.
PH the most according to claim 1 and the preparation method of temperature dual sensitiveness intelligent nano-gel, its
In, described crosslinking agent is selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, diethylene glycol double third
Olefin(e) acid ester, tirethylene glycol double methacrylate and polyethyleneglycol diacrylate.
PH the most according to claim 1 and the preparation method of temperature dual sensitiveness intelligent nano-gel, its
In, described oxidant is selected from ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate.
PH the most according to claim 1 and the preparation method of temperature dual sensitiveness intelligent nano-gel, its
In, described reducing agent closes Sodium Thiosulfate selected from sodium hydrogensulfite, sodium sulfite, sodium thiosulfate and formaldehyde.
PH the most according to claim 1 and the preparation method of temperature dual sensitiveness intelligent nano-gel, its
In, the average grain diameter of described intelligent nano-gel reverse micro emulsion is 40-80nm.
8. pH and a temperature dual sensitiveness intelligent nano-gel, it is by described in any one of claim 1-7
The preparation method of pH and temperature dual sensitiveness intelligent nano-gel prepares.
PH the most according to claim 8 and temperature dual sensitiveness intelligent nano-gel, wherein, this pH and
The gel strength of temperature dual sensitiveness intelligent nano-gel is 5-15Pa s.
PH the most according to claim 8 and temperature dual sensitiveness intelligent nano-gel, wherein, this pH
It is 80-500g/g with the equilibrium water absorption of temperature dual sensitiveness intelligent nano-gel, is the NaCl of 5wt% to concentration
The balance salt absorbing rate of solution is 25-35g/g, is the CaCl of 5wt% to concentration2The balance salt absorbing rate of solution is 10-20g/g,
It is the MgCl of 5wt% to concentration2The balance salt absorbing rate of solution is 15-25g/g.
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| CN105218835B (en) * | 2015-09-25 | 2017-12-12 | 西北师范大学 | A kind of preparation of keratin base sensitive high-molecular gel and the application as pharmaceutical carrier |
| CN107952108B (en) * | 2017-11-13 | 2021-05-28 | 广西达庆生物科技有限公司 | Liquid gel dressing for resisting infection and contraception and preparation method thereof |
| CN109964927B (en) * | 2019-04-04 | 2021-12-03 | 江南大学 | Preparation method of temperature/pH dual-response nano antibacterial system |
| CN112112599B (en) * | 2020-10-09 | 2022-05-06 | 西南石油大学 | Low-viscosity plugging system for fractured reservoir and preparation method thereof |
| CN114058032B (en) * | 2021-12-09 | 2023-06-02 | 广东华美众源生物科技有限公司 | Dual-response nano composite hydrogel and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1834125A (en) * | 2005-03-18 | 2006-09-20 | 中国科学院理化技术研究所 | Template copolymerization synthesis method of semi-interpenetrating network reversible pH sensitive hydrogel |
| CN103242594A (en) * | 2013-05-14 | 2013-08-14 | 中国科学院长春应用化学研究所 | Polymer hydrogel microspheres and preparation method thereof |
-
2014
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1454924A (en) * | 2003-05-15 | 2003-11-12 | 复旦大学 | Multifunctional organic-inorganic composite polymeric microball and preparing method thereof |
| CN1834125A (en) * | 2005-03-18 | 2006-09-20 | 中国科学院理化技术研究所 | Template copolymerization synthesis method of semi-interpenetrating network reversible pH sensitive hydrogel |
| CN103242594A (en) * | 2013-05-14 | 2013-08-14 | 中国科学院长春应用化学研究所 | Polymer hydrogel microspheres and preparation method thereof |
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